JP4909012B2 - Design coating film formation method and coating film structure - Google Patents

Description

  The present invention relates to a design coating film forming method and a coating film structure using a multicolor paint.

  For example, a multi-pattern paint is well known as a paint in which granular gel is stably dispersed in a dispersion medium. The multicolored paint is a paint that can produce various patterns of two or more colors with a single painting, and is mainly used for painting buildings and the like.

  As a coating method using a multicolored paint, Patent Document 1 includes, as main components, a polymer obtained by polymerizing at least one monomer selected from vinyl toluene, butadiene, styrene, and an acrylic monomer, a pigment, and an organic solvent. After coating and drying a multicolored paint containing at least one kind of enamel-dispersed particles obtained by mixing and dispersing the composition to enamel and dispersing it in an aqueous dispersion medium, the concealment rate of the dried coating film is on it. A multi-pattern paint finishing method is described in which a clear paint that is 0.5 or less is applied.

  According to such a paint finishing method, it is possible to maintain the initial coating state without causing deterioration of the coating film over time or cracking between the pattern particles even in outdoor use, and a deep finish appearance by clear coating However, since the multicolored coating film is formed by fusing the pattern particles, it cannot be denied that it is insufficient for long-term durability.

  Patent Document 2 discloses a natural stone-like paint composition comprising, as main components, a pattern color-forming dispersed phase particle having a specific particle size distribution composed of a plurality of colors and a transparent dispersion medium capable of dispersing the dispersed phase particle in a particle state. A natural stone-like coating method characterized by coating an object on an undercoat layer is described. According to such a coating method, it is possible to form a layered coating film having a natural stone tone and full of volume without requiring special skills such as a special coating machine or a skilled coating specialist. In this coating method, there are few variations in design, and in order to respond to diversified user preferences, it is necessary to develop a coating system that forms a coating film exhibiting unique design properties.

JP-A-9-57186 JP 2003-154308 A

  The objective of this invention is providing the coating-film formation method excellent in the designability using a colorful pattern coating material.

As a result of intensive studies on the above problems, the inventors of the present invention applied a colorful pattern paint on a coating film containing a glitter pigment so as to have a concealment ratio within a specific range, thereby forming a glitter coating film as a base. The present inventors have found that the resulting glittering feeling can be appropriately imparted to the multicolored coating film, and have reached the present invention. That is, the present invention
1.
On the glitter coating film formed by applying the paint (I) containing the glitter pigment, the pigment composition comprises the colored paint particles (A) and the coating film forming component (B), and the colored paint particles (A) A multi- pattern paint (II), which is formed by encapsulating a water-based resin composition (a1) and a colorant (a2) in a polysaccharide metal salt gel, is provided with a multi-pattern paint film. A method for forming a designable coating film, comprising: coating the multicolored paint (II) so that a concealing rate of the formed coating film is within a range of 10 to 70%. Method,
2.
The coating composition (I) containing the glitter pigment contains the glitter pigment in the range of 0.01 to 100% by mass with respect to the resin solid content contained in the paint (I). Method,
3.
The method for forming a designable coating film according to Item 1 or 2, wherein the paint (I) containing the glitter pigment further contains a color pigment,
4).
The method for forming a designable coating film according to any one of items 1 to 3, wherein the paint (I) containing the glitter pigment further contains an ultraviolet absorber and / or a light stabilizer,
5.
Monovalent in which the colored coating particles (A) can form an aqueous coating composition containing the aqueous resin (a1), the colorant (a2) and the water-soluble polysaccharide, with the water-soluble polysaccharide and a water-insoluble or hardly soluble salt. Or the designable coating-film formation method of any one of 1 thru | or 4 which is obtained by making it contact with the aqueous medium containing a polyvalent metal ion,
6).
The colored coating particle (A) contains a reactive functional group (x), and the coating film forming component (B) contains a reactive functional group (y) that can react with the reactive functional group (x). The design coating film forming method according to any one of items 1 to 5 ,
7).
Both the colored paint particles (A) and the coating film forming component (B) contain a carbonyl group-containing aqueous resin, and the colored paint particles (A) and / or the coating film forming component (B) contain a hydrazine derivative. The design coating film forming method according to any one of 1 to 6, characterized in that,
8).
A coating film structure excellent in design properties obtained by the design coating film forming method according to any one of items 1 to 7,
About.

  According to the design coating film forming method of the present invention, since a specific multi-pattern coating film is provided on the coating film containing the glitter pigment, the design rich in change depending on the viewing angle and direction, the light irradiation method, etc. Can demonstrate its sexuality. When the design coating film of the present invention is viewed from the front, the multi-pattern coating film appears to shine brilliantly due to the glittering pigment of the coating film applied beneath it, and the appearance is rich in variations with depth. Can do.

  The coated surface applied to the design coating film forming method of the present invention is not particularly limited. For example, gypsum board, concrete wall, mortar wall, slate plate, PC plate, ALC plate, cement calcium silicate plate Surfaces of base materials such as wood, stone, plastic moldings, metal workpieces, acrylic resins, acrylic urethane resins, polyurethane resins, fluororesins, acrylic silicon resins, acetic acid provided on these substrates Examples thereof include a coating surface such as vinyl resin and epoxy resin, and a wallpaper surface made of materials such as polyvinyl chloride, polyolefin, paper, and cloth.

  The paint (I) containing the glitter pigment used in the method of the present invention may be a clear paint or a colored paint as long as it contains the glitter pigment. (Hereafter, it may be abbreviated as glitter paint (I)).

  As the bright pigment, conventionally known pigments can be used. Specifically, metallic pigments such as aluminum powder, bronze powder, copper powder, tin powder, iron phosphide, zinc powder; mica, metal oxide coating Examples thereof include mica powder, metal iron oxide-coated alumina flakes, metal oxide-coated silica flakes, and pearlescent pigments such as mica-like iron oxide, and these can be used alone or in combination of two or more. .

  The amount of the glitter pigment contained in the glitter paint (I) can be appropriately adjusted depending on the kind of the glitter pigment, but generally, the amount of the glitter pigment is 0.1% relative to the resin solid content contained in the glitter paint (I). When it is in the range of 01 to 100% by mass, particularly 0.2 to 70% by mass, the glittering coating film can appropriately impart a glittering feeling to the multicolored coating film provided thereon. is there.

  In addition to the glittering pigment, a coloring pigment or an extender pigment may be added to the glittering paint (I).

  Examples of the color pigment include white pigments such as titanium oxide; black pigments such as carbon black, acetylene black, lamp black, bone black, graphite, iron black, and aniline black; yellow iron oxide, titanium yellow, monoazo yellow, and condensed azo. Yellow pigments such as yellow, azomethine yellow, bismuth vanadate, benzimidazolone, isoindolinone, isoindoline, quinophthalone, benzidine yellow, permanent yellow; orange pigments such as permanent orange; red iron oxide, naphthol AS azo red, ansanthrone , Anthraquinonyl red, perylene maroon, quinacridone red pigment, diketopyrrolopyrrole, watching red, permanent red and other red pigments; cobalt purple, quinacridone violet, dioxadi Violet pigments such as violet; like green pigment such as phthalocyanine green; cobalt blue, phthalocyanine blue, blue pigments such as vat blue.

  Examples of extender pigments include barita powder, precipitated barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, white carbon, diatomaceous earth, talc, magnesium carbonate, alumina white, gloss white, silica sand, and quartz powder.

  These color pigments and extender pigments can be used alone or in combination of two or more. The titanium dioxide as the white pigment includes functional titanium dioxide such as micro titanium having an average particle diameter of 10 to 80 nm and anatase type titanium dioxide having photocatalytic activity.

  When a coloring pigment is used in the glitter paint (I), the blending amount thereof is in the range of 1 to 200% by weight, particularly 5 to 150% by weight, based on the resin solid content contained in the glitter paint (I). If it is inside, the glittering feeling of the glittering pigment, the color of the colored pigment, and the multicolored paint film provided on it merge to create a sparkling and deep appearance from inside the multicolored paint film. Can be preferred.

  As the resin component contained in the glitter paint (I), those known as conventionally known binder components can be used without limitation, and may be a crosslinked type or a non-crosslinked type, or an organic solvent. It may be a mold or an aqueous system. The resin type is not particularly limited. Specifically, for example, acrylic resin, polyolefin resin, silicon resin, polyurethane resin, epoxy resin, phenol resin, polyester resin, alkyd resin, polycarbonate These resins can be used, and these can be used alone or in combination of two or more. These resins may be modified like, for example, urethane-modified acrylic resin, or may be graft-polymerized.

  The resin component contained in the glitter paint (I) is an aqueous resin, which is suitable from the viewpoint of adhesion between both when a later-described multicolored paint is aqueous.

  Moreover, it is suitable for the said glittering paint (I) to further contain a ultraviolet absorber and / or a light stabilizer.

  Thereby, with the improvement in the weather resistance of the glittering coating film, there is an effect of further enhancing the durability of the design coating film obtained by the coating method of the present invention.

  Examples of ultraviolet absorbers include salicylic acid derivatives such as phenyl salicylate, p-octylphenyl salicylate, 4-t-butylphenyl salicylate; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2,2'-dihydroxy- 4,4'-dimethoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, sodium 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2, , 2 ', 4,4'-tetrahydro Xylbenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, resorcinol monobenzoate, 2,4-dibenzoyl resorcinol, 4,6-dibenzoyl resorcinol, hydroxy Benzophenones such as dodecylbenzophenone and 2,2'-dihydroxy-4 (3-methacryloxy-2-hydroxypropoxy) benzophenone; benzotriazoles such as 2- (2'-hydroxy-5'-methylphenyl) benzotriazole And other compounds such as oxalic anilide and cyanoacrylate.

  As the light stabilizer, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl)- 5-chlorobenzotriazole, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6- Tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate 1- (2-hydroxyethyl) -4-hydroxy-2 , 2,6,6-tetramethylpiperidine polycondensate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, bis- (2,2 ′, 6, 6'-tetramethyl-4-pi Lysinyl) Sebate - DOO, 4-benzoyloxy -2,2', 6,6'-tetramethyl piperidine, and the like.

  The said ultraviolet absorber and / or light stabilizer may be used independently, can also be selected suitably and can be used in combination.

  The proportion of the ultraviolet absorber used is in the range of 0.1 to 5.0 mass%, preferably 0.2 to 2.0 mass%, based on the resin solid content contained in the glittering paint (I). The light stabilizer is used in a proportion of 0.1 to 5.0% by mass, preferably 0.2 to 3.0% by mass, based on the resin solid content contained in the glittering paint (I). It is preferable to be within the range.

  The glitter paint (I) is an antifoaming agent, a curing catalyst, a pigment dispersant, a surfactant, a film-forming aid, a viscosity modifier, a neutralizing agent, an antiseptic, an antifungal agent, an antifreezing agent, and formaldehyde adsorption. A coating additive such as an agent can be included as necessary.

  The glitter paint (I) can be applied using a coating means known per se, for example, using a coating instrument such as a roller, air spray, airless spray, lysine gun, universal gun, brush, or iron. be able to. Moreover, when using a roller, a wool roller, a sand-bone roller, etc. can be used.

The coating amount of the glitter paint (I) can be changed depending on the composition of the glitter paint used and the state of the multicolored paint film, but usually 10 to 500 g / m ² , preferably 20 to 350 g as the solid content of the paint. It is desirable to adjust within the range of / m ² .

  The formed coating film can be dried by any of heat drying, forced drying, or room temperature drying depending on the type of paint used.

  In the method of the present invention, the multicolor paint (II) is applied on the glittering paint film obtained above so that the concealment ratio of the paint film formed is in the range of 10 to 70%, preferably 20 to 65%. It is characterized by doing.

  In the present invention, it is important that the multicolor pattern coating film provided on the glitter coating film has its own concealment ratio within the above range, and the coating amount and the material of the multicolor pattern paint for forming the multicolor pattern coating film. Etc. can be arbitrarily selected.

  The test piece for calculating the concealment rate (%) is prepared by fixing the concealment rate test paper described in Method B (Concealment rate test paper) of JIS K 5600 4-1 horizontally on a flat glass plate. Then, the multi-color paint is applied thereon, the coating surface is leveled upward, and dried for 48 hours under conditions of an air temperature of 23 ° C. and a relative humidity of 60%.

In this specification, the concealment rate (%) is in accordance with JIS K 56004-1 Method B (Concealment rate test paper), white (Y _W ) and black background (Y _B ) of the test piece (coated opacity test paper). ) the point on the randomly selected each four places, to measure the tristimulus values of the points, to calculate the average of the tristimulus values Y _W and Y _B. Thereafter, a value obtained by calculating Y _B / Y _W at a 100-minute rate is defined as a concealment rate.

  In the method of the present invention, as the multicolored paint (II) for forming the multicolored paint film, a multicolor paint containing at least two colored paint particles (A) and a paint film forming component (B) is used. However, it is suitable from the viewpoint of the balance between the design properties of the final design coating film and the physical properties of the coating film.

  The colored paint particles (A) are not particularly limited, such as materials and production methods, and conventionally known ones can be used, which may be water-based or solvent-based. For example, it is suitable to use an aqueous coating composition containing an aqueous resin (a1) and a colorant (a2) in a polysaccharide metal salt gel.

  The aqueous resin (a1) contained in the aqueous coating composition contributes to the durability of the colored coating particles (A), and a resin that can be dissolved or dispersed in water is used. The resin type is not particularly limited, and specifically, for example, it can be appropriately selected from the resins listed in the resin contained in the glitter paint (I).

  When the aqueous resin (a1) is in the form of dispersed particles, the aqueous resin (a1) may be a single layer or a multilayer such as a core / shell type. In addition, the aqueous resin (a1) can be a resin having an anionic group, for example, a carboxyl group as a hydrophilic group from the viewpoint of production stability of the colored paint particles (A). In this case, the resin is Examples of the neutralizing agent that may be neutralized and used in this case include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, dimethylaminoethanol, 2-methyl-2-amino-1- Examples include amines such as propanol and ammonia, and these can be used alone or in combination of two or more.

  The aqueous resin (a1) is preferably an acrylic resin from the viewpoints of durability, weather resistance, and the like of the colored paint particles (A).

  Examples of such acrylic resins include resins obtained by copolymerizing polymerizable unsaturated monomers. Examples of such polymerizable unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) ) Acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, etc. Linear or branched alkyl (meth) acrylate; Cyclohexyl (meth) acrylate, cycloaliphatic alkyl (meth) acrylate such as isobornyl (meth) acrylate; Aralkyl (meth) acrylate such as benzyl (meth) acrylate Alkoxyalkyl (meth) acrylates such as 2-methoxyethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate; Perfluoroalkyl (meth) acrylate; N, N such as N, N-diethylaminoethyl (meth) acrylate -Dialkylaminoalkyl (meth) acrylate; (meth) acrylamide; (meth) acrylonitrile; vinyl ester compounds such as vinyl acetate and vinyl propionate; vinyl aromatic compounds such as styrene and α-methylstyrene; allyl (meth) acrylate; Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, trimethylol propylene N-tri (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tetra (Meth) acrylate, glycerol di (meth) acrylate, 1,1,1-trishydroxymethylethane di (meth) acrylate, 1,1,1-trishydroxymethylethanetri (meth) acrylate, 1,1,1- Polyvinyl compounds having at least two polymerizable unsaturated groups in one molecule such as trishydroxymethylpropane tri (meth) acrylate, triallyl isocyanurate, diallyl terephthalate, divinylbenzene, etc .; 2-hydroxyethyl (meth) acrylate , 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as hydroxybutyl (meth) acrylate, allyl alcohol, and ε-caprolactone modification of the above hydroxyalkyl (meth) acrylate Body, hydroxyl group-containing polymerizable unsaturated monomer such as polyoxyethylene chain-containing (meth) acrylate having molecular terminal hydroxyl group; carboxyl group-containing polymerization such as (meth) acrylic acid, maleic acid, crotonic acid, β-carboxyethyl acrylate, etc. Unsaturated monomers; (meth) acrolein, formylstyrene, vinyl alkyl ketones having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone), acetoacetoxyethyl (meth) a Carbonyl group-containing polymerizable unsaturated monomers such as relate, acetoacetoxyallyl ester, diacetone (meth) acrylamide; glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate , 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, epoxy group-containing polymerizable unsaturated monomers such as allyl glycidyl ether; isocyanate ethyl (meth) acrylate, m-iso Isocyanate group-containing polymerizable unsaturated monomers such as propenyl-α, α-dimethylbenzyl isocyanate; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrime Alkoxysilyl group-containing polymerizable unsaturated monomers such as toxisilane, γ-methacryloyloxypropyltriethoxysilane; epoxy group-containing polymerizable unsaturated monomers or reaction products of hydroxyl group-containing polymerizable unsaturated monomers with unsaturated fatty acids, dicyclo Examples thereof include oxidizable curable group-containing polymerizable unsaturated monomers such as pentenyloxyethyl (meth) acrylate, dicyclopentenyloxypropyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and the like. These can be used in combination.

  The polymerization method of the monomer is not particularly limited. For example, according to a general emulsion polymerization method, an acrylic resin can be easily produced by (co) polymerizing the monomer in the presence of an emulsifier. Can do.

  As the emulsifier used in the production of the acrylic resin, known emulsifiers can be used. Examples of applicable emulsifiers include anionic emulsifiers, nonionic emulsifiers and amphoteric emulsifiers. Can do.

  Examples of the anionic emulsifier include diammonium dodecyl diphenyl ether disulfonate, sodium dodecyl diphenyl ether disulfonate, calcium dodecyl diphenyl ether disulfonate, alkyl diphenyl ether disulfonate such as sodium alkyl diphenyl ether disulfonate; sodium dodecyl benzene sulfonate, dodecyl benzene sulfonic acid Alkyl benzene sulfonates such as ammonium; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; aliphatic carboxylates such as fatty acid sodium and potassium oleate; sulfate salts containing polyoxyalkylene units (for example, polyoxyethylene alkyl) Sodium ether sulfate, polyoxyethylene alkyl ether sulfate Polyoxyethylene alkyl ether sulfates such as ammonium; polyoxyethylene alkylphenyl ether sulfate sodium, polyoxyethylene alkylphenyl ether sulfates such as ammonium polyoxyethylene alkylphenyl ether sulfate; polyoxyethylene polycyclic sodium phenyl ether sulfate; Polyoxyethylene polycyclic phenyl ether sulfates such as polyoxyethylene polycyclic phenyl ether ammonium sulfate); Naphthalene sulfonic acid formalin condensate such as sodium naphthalene sulfonic acid formalin condensate salt; Sodium dialkyl sulfosuccinate, monoalkyl succinate Alkyl succinate sulfonates such as disodium sulfonate, and the like. It may be used in combination of two or more.

  Examples of nonionic emulsifiers include polyoxyalkylene unit-containing ether compounds (for example, polyoxyalkylene alkyl ether compounds such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene tridecyl ether, polyoxyethylene oleyl ether). Polyoxyalkylene alkyl phenyl ether compounds such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; polyoxyalkylene polycyclic phenyl ether compounds such as polyoxyethylene polycyclic phenyl ether); polyoxyethylene monolaurate Polyoxyalkylene alkyl ester compounds such as polyoxyethylene monostearate and polyoxyethylene monooleate; Polyoxyalkylene alkylamine compounds such as reoxyethylene alkylamine; sorbitan compounds such as sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, etc. These can be used alone or in combination of two or more.

  Examples of amphoteric emulsifiers include dimethylalkyl betaines, dimethylalkyl lauryl betaines, and alkyl glycines.

  As the emulsifier, a reactive emulsifier containing both a polymerizable unsaturated group and an anionic group or nonionic group in the molecule can also be used.

  The usage-amount of the said emulsifier is 0.5-6 mass% normally on the basis of the total mass of a polymerizable unsaturated monomer, Preferably it can exist in the range of 1-4 mass%.

  As the colorant (a2) that can be contained in the colored paint particles (A), a color pigment and a dye can be used. As a coloring pigment, it can select suitably from what was illustrated by description of the said glittering paint, and can be used individually or in combination of 2 or more types.

  On the other hand, examples of the dye include azo dyes such as monoazo dyes, polyazo dyes, metal complex azo dyes, pyrazolone azo dyes, stilbene azo dyes and thiazole azo dyes; anthraquino dyes such as anthraquinone derivatives and anthrone derivatives; indigo derivatives and thioindigo derivatives Indigoid dyes such as: phthalocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes; quinoneimine dyes such as azine dyes, oxazine dyes, thiazine dyes; polymethine (or cyanine) dyes, adimethine dyes, etc. Methine dyes; quinoline dyes; nitro dyes; nitrone dyes; benzoquinone and naphthyquinone dyes; naphthalimide dyes; perinone dyes, and the like. Not to be able to use. These colorants can be used alone or in combination of two or more according to the target color.

  In the colored paint particles (A), an extender can be used together with the colorant (a2). The extender pigment can be appropriately selected from those listed in the description of the glitter paint (I), and can be used alone or in combination of two or more.

  The blending amount of the colorant (a2) is usually 0.01 to from the viewpoint of the colorability, specific gravity, durability, water resistance and the like of the colored paint particles (A), based on the mass of the aqueous resin (a1). It is suitable to be in the range of 500% by weight, preferably 0.05 to 400% by weight.

  The colored paint particles (A) form, for example, an aqueous paint composition containing an aqueous resin (a1), a colorant (a2) and a water-soluble polysaccharide, and form a water-insoluble or sparingly soluble salt with the water-soluble polysaccharide. It can be obtained by contacting with an aqueous medium containing monovalent or polyvalent metal ions, thereby forming colored paint particles in which the aqueous paint composition is encapsulated in a polysaccharide metal salt gel. be able to.

  The water-soluble polysaccharide is a polysaccharide capable of changing to a water-insoluble or sparingly soluble gel when contacted with a monovalent or polyvalent metal ion in an aqueous medium, generally about 3,000 to about 3,000. Those having a number average molecular weight in the range of 2,000,000 and exhibiting a water solubility of about 10 g / L (25 ° C.) or more are preferred. Specifically, for example, alginic acid or an alkali metal salt thereof, Gellan gum, carrageenan and the like can be mentioned, and these can be used alone or in combination of two or more.

  The water-soluble polysaccharide is the stability of the colored paint particles (A) in water, the handleability when producing the colored paint particles (A), and the water resistance of the coating film formed from the paint containing the colored paint particles (A). From the standpoint of properties, it is usually 0.1 to 7% by mass, preferably 0.1 to 5% by mass, based on the total mass of the aqueous resin (a1) and the water-soluble polysaccharide. .

  The above-mentioned aqueous coating composition further comprises a specific gravity adjusting material such as balloon particles, an antifoaming agent, a curing catalyst, a pigment dispersant, a fragrance, a deodorizing agent, an antibacterial agent, a neutralizing agent, a surfactant, if necessary. Aqueous water repellent, dispersant, antiseptic, antifungal agent, antifreezing agent, UV absorber, light stabilizer, film-forming aid, zinc whisker, formaldehyde adsorbent, antimony trioxide, antimony pentoxide, hydroxylation A flame retardant such as aluminum can be contained.

  In the present invention, the aqueous coating composition for producing the colored coating particles (A) is, for example, a paste of an aqueous resin (a1) and a coloring agent (a2) and an aqueous solution of a water-soluble polysaccharide as appropriate. It can prepare by mixing with the component of these.

  The metal compound used as a source of metal ions used when the aqueous coating composition is made into a granular gel is desirably 0.005 mg or more, particularly 0.08 mg or more in 100 g of water at 25 ° C., For example, monovalent metals such as potassium and sodium, magnesium, calcium, strontium, barium, chromium, molybdenum, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, copper, zinc, cadmium, aluminum, cerium, etc. Examples thereof include hydroxides, oxides, carbonates, chlorides and sulfides of valent metals, and these can be used alone or in combination of two or more.

  In the coating method of the present invention, the metal compound is desirably a hydroxide, an oxide, or a carbonate from the viewpoint of the water resistance of the finally formed design coating film, and is a calcium salt. More desirable.

  In the present invention, when calcium hydroxide is used as the metal compound, the water resistance of the design coating film is improved, which is particularly preferable.

  An aqueous medium containing a monovalent or polyvalent metal ion can be prepared by dissolving at least a part of the metal compound in the aqueous medium. At that time, the metal compound does not need to be completely dissolved in the aqueous medium, and may be partially dissolved. The content of the metal compound in the aqueous medium containing the metal compound is usually 0.05 to 15% by mass, preferably 0.1 to 10% by mass.

  The water-based paint composition can form colored paint particles (A) by contacting with an aqueous medium containing metal ions derived from the metal compound. This contact can be performed, for example, from the tip of a syringe. A method in which an aqueous coating composition is dropped into an aqueous medium; a method in which the aqueous coating composition is dispersed using centrifugal force and is dropped into the aqueous medium; an aqueous coating composition is atomized from the tip of a spray nozzle to form an aqueous A method of dropping in a medium; a method of adding an aqueous coating composition into an aqueous medium and stirring and mixing with a disperser.

  The size (major axis) of the colored paint particles (A) formed as described above is not particularly limited and can be appropriately changed according to the design required for the multicolor paint (II). For example, it can be adjusted depending on the composition of the aqueous coating composition, the concentration of metal ions in the aqueous medium, the manner in which the aqueous coating composition is dropped onto the aqueous medium, and the like.

  The resulting colored paint particles (A) can be filtered off from an aqueous medium containing metal ions using, for example, a wire mesh having a mesh of an appropriate size.

  The above-mentioned multicolored pattern paint (II) is a colored paint particle (from the viewpoint of durability as a designable paint film obtained by the coating method of the present invention while ensuring the coating film properties such as water resistance of the multicolored pattern paint film. It is desirable to contain a film-forming component (B) in addition to A). The coating film forming component (B) itself has film-forming properties, and may be either non-crosslinked type or crosslinked type.

  In the present invention, from the viewpoints of affinity with the colored paint particles (A) and storage stability as the multicolored paint (II), when the colored paint particles (A) contain an aqueous resin (a1), a coating film is formed. The component (B) is preferably an aqueous composition comprising the aqueous resin (b1).

  As said water-based resin (b1), what is generally used as a resin binder in the field of water-based paint can be used. For example, it is appropriately selected from those described above as water-based resin (a1) in colored paint particles (A). Can be used in

  In the present invention, the water-based paint composition and the coating film-forming component (B) contained in the colored paint particles (A) contain various functional groups (x) and (y) that can react with each other. Since the water resistance of the coating film and the design coating film obtained by the coating method of the present invention can be improved, the colored coating particle (A) contains a reactive functional group (x), The coating film-forming component (B) preferably contains a reactive functional group (y) that can react with the reactive functional group (x).

  As a combination of the reactive functional group (x) contained in the aqueous coating composition contained in the colored paint particles (A) and the reactive functional group (y) contained in the coating film forming component (B), The combination is not particularly limited as long as it is a combination that can react with each other under the drying conditions of the coating film. Specifically, for example, a hydroxyl group and an isocyanate group, a hydroxyl group and an alkyl ether group, a hydroxyl group and an imino group, and a carboxyl group Examples include combinations of epoxy groups, amino groups and epoxy groups, amide groups and epoxy groups, carbonyl groups and hydrazine groups, carbonyl groups and hydrazide groups, carbonyl groups and semicarbazide groups, and carbonyl groups and bisacetyldihydrazone groups. A combination of a carbonyl group and a hydrazide group is preferable because it can be cross-linked at one room temperature.

  As the multicolored paint, the colored paint particles (A) and the coating film forming component (B) both contain a resin having a reactive functional group (x), and the colored paint particles (A) and / or the coating film forming component (B) can also be a form which has a crosslinking agent which has the reactive functional group (y) which can react with the reactive functional group (x).

  In the method of the present invention, the colored paint particles (A) and the coating film forming component (B) are both carbonyl group-containing aqueous from the viewpoints of water resistance, weather resistance, storage stability as a multicolored paint, and the like. It is desirable that the resin contains a resin and that the colored paint particles (A) and / or the coating film forming component (B) contain a hydrazine derivative.

  Examples of the hydrazine derivative for reacting with the carbonyl group that can be contained in the colored paint particles (A) or the coating film forming component (B) include hydrazine, hydrazine hydrate, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, Dihydrazides of saturated aliphatic carboxylic acids having 2 to 18 carbon atoms such as glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide; dihydrazides of monoolefinic unsaturated dicarboxylic acids such as maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide; Phthalic acid, terephthalic acid or isophthalic acid dihydrazide; pyromellitic acid dihydrazide, trihydrazide or tetrahydrazide; nitrilotriacetic acid trihydrazide, citric acid trihydrazide, 1,2,4-benzenetrihydra Ethylenediaminetetraacetic acid tetrahydrazide, 1,4,5,8-naphthoic acid tetrahydrazide; polyhydrazide obtained by reacting a low polymer having a carboxylic acid lower alkyl ester group with hydrazine or hydrazine hydrate (hydrazine hydride) Etc .; Carbonic dihydrazide, bissemicarbazide; Diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate and polyisocyanate compounds derived therefrom are reacted with N, N-substituted hydrazines such as N, N-dimethylhydrazine and the hydrazides exemplified above in excess. A polyfunctional semicarbazide obtained by the above process; isoforms in a reaction product of the polyisocyanate compound and an active hydrogen compound containing a hydrophilic group such as polyether polyols and polyethylene glycol monoalkyl ethers; An aqueous polyfunctional semicarbazide obtained by excessively reacting the above-exemplified dihydrazide with an anate group; a mixture of the polyfunctional semicarbazide and an aqueous polyfunctional semicarbazide; bisacetyldihydrazone, and the like. These can be used in combination.

  In the present invention, the coating film forming component (B) may form a colored coating film or may form a clear coating film. Coloring agents can be included.

  The colorant that can be contained in the coating film forming component (B) can be appropriately selected from those exemplified above as the colorant in the colored paint particles (A). Further, from the viewpoint of improving the drying property of the multicolor pattern coating film, improving the appropriate gloss, and improving the touch feeling, it is desirable to incorporate the extender pigment as described above into the coating film forming component (B).

  When mix | blending a coloring agent and / or an extender pigment with a coating-film formation component (B), the total compounding quantity is 5-300 mass% normally with respect to the resin solid content contained in a coating-film formation component (B). , Preferably 10 to 200% by mass, more preferably 15 to 150% by mass.

  The blending ratio of the colored paint particles (A) and the coating film forming component (B) is such that the concealment ratio of the multicolored pattern coating film is in the above range, and the water resistance of the design coating film finally obtained, It is 1/99 to 60/40, preferably 10/90 to 50/50, more preferably 20/80 to 45/55 in terms of the solid content mass ratio of the colored paint particles (A) / the coating film forming component (B). Can be within range.

  The multicolored paint (II) can contain paint additives as required.

  Examples of the additives for paint include neutralizers, viscosity modifiers, balloon particles, anti-settling agents, antistatic agents, softeners, antibacterial agents, fragrances, curing catalysts, pH adjusters, humidity control agents, powders or fine particles Activated carbon, photocatalytic titanium oxide, aqueous water repellent, dispersant, antifoaming agent, antiseptic, antifungal agent, antifreezing agent, UV absorber, light stabilizer, film-forming aid, zinc whisker, curing acceleration And flame retardants such as agents, aldehyde adsorbents, waxes, antimony trioxide, antimony pentoxide, and aluminum hydroxide.

The above-mentioned multicolor pattern paint (II) can be applied by using a coating means known per se, for example, using a painting tool such as a roller, air spray, airless spray, lysine gun, universal gun, brush, or iron. It can be carried out. Moreover, when using a roller, a wool roller, a sand-bone roller, etc. can be used, and as a coating amount, it adjusts suitably so that the concealment rate of the multi-colored coating film formed may be in the said range. In general, however, the solid content of the coating material should be adjusted to ^{20 to} 500 g / m ² , preferably 30 to 350 g / m ² .

  The formed coating film can be dried by any of heat drying, forced drying, or room temperature drying depending on the composition of the coating composition used.

  Moreover, in the designable coating-film formation method of this invention, you may provide the process of apply | coating undercoat paint and drying before applying a glittering paint.

  The undercoat paint used here can be appropriately selected according to the type and state of the substrate surface, and for example, an undercoat paint such as a sealer or a base conditioner can be used. It is also possible to apply a normal top coat as a base forming paint for a multi-color paint.

  Examples of the top coat for forming the base include, for example, an aqueous resin composed of a resin type such as an acrylic resin, a polyolefin resin, a silicon resin, a polyurethane resin, an epoxy resin, a phenol resin, a polyester resin, and an alkyd resin. Or the coating material which contains solvent-type resin as a resin binder can be mentioned, It is preferable to use the coating material which contains water-system resin.

  When applying the undercoat paint, two or more kinds of undercoat paints can be repeated as necessary.

  The undercoat paint can be applied by using a coating means known per se, for example, using a coating tool such as a roller, air spray, airless spray, lysine gun, universal gun, brush, or iron. .

The coating amount of the primer coating can be varied according to the types of base material to be coated, usually 10 to 1000 g / ^{m 2} as a solid content, it preferably in the range of 14~500g / ^{m 2} Can do.

  The formed undercoat coating film can be dried by any of heat drying, forced drying, or room temperature drying depending on the type of the undercoat used.

  Hereinafter, the present invention will be described in more detail with reference to examples. “Part” and “%” indicate “part by mass” and “% by mass” unless otherwise specified.

Production of carbonyl group-containing emulsion Production Example 1
In a 4-liter flask having a capacity of 2 liters, 285 parts of deionized water and 1 part of “NEWCOL707-SF” (trade name, manufactured by Nippon Emulsifier Co., Ltd., an anionic surfactant having a polyoxyethylene chain, non-volatile content of 30%) In addition, after nitrogen substitution, the temperature was kept at 85 ° C. Add 3% of the pre-emulsion obtained by emulsifying the following composition and 41 parts of 123 parts of ammonium persulfate aqueous solution in which 3 parts of ammonium persulfate was dissolved in 120 parts of deionized water. After 20 minutes, the remaining pre-emulsion and the remaining aqueous ammonium persulfate solution were added dropwise to the flask over 4 hours.
Deionized water 368 parts Styrene 150 parts Methyl methacrylate 413 parts n-Butyl acrylate 240 parts 2-ethylhexyl acrylate 150 parts Diacetone acrylamide 20 parts 1,6-hexanediol diacrylate 5 parts 2-hydroxyethyl acrylate 20 parts Acrylic acid 2 parts “NEWCOL707-SF” After 66 parts of the dropwise addition, this was further maintained at 85 ° C. for 2 hours and then cooled to 40-60 ° C. Subsequently, the pH was adjusted to 8 to 9 with aqueous ammonia to obtain a carbonyl group-containing emulsion (a1) having a solid content of 55%, an average particle size of 170 nm, and a pH of 8.3.

Production of white pigment paste Production Example 2
The following components were charged in a 1 liter stainless steel container, and stirred with a disper for 30 minutes until uniform, to obtain a white pigment paste (b1).
Water 225 parts “Slulloff 72N” (Note 1) 15 parts “DISPER BYK-190” (Note 2) 30 parts “SN Deformer 380” (Note 3) 15 parts “TITANIX JR-605” (Note 4) 500 parts (Note) 1) “Suraoff 72N”: trade name, manufactured by Takeda Pharmaceutical Co., Ltd., preservative (Note 2) “DISPER BYK-190”: trade name, manufactured by BYK Chemie, pigment dispersant (Note 3) “SN Deformer 380 ": Trade name, manufactured by San Nopco, defoaming agent (Note 4)" TITANIX JR-605 ": trade name, manufactured by Teika, titanium white.

Production of undercoat paint Production examples 3 to 5
The components shown in Table 1 below were charged into a 1 liter stainless steel container while sequentially stirring, and then further stirred to prepare undercoat paints (A-1) to (A-3).

(Note 5) “TEXANOL”: trade name, manufactured by Eastman Chemical Company, 2,2,4-trimethylpentanediol monoisobutyrate, film-forming aid,
(Note 6) “Iriodin 103W2”: trade name, manufactured by Merck & Co., titanium dioxide-coated mica pigment,
(Note 7) “TINUVINE 123”: trade name, manufactured by Ciba Specialty Chemicals, piperazine light stabilizer,
(Note 8) “TINUVINE 384-2”: trade name, manufactured by Ciba Specialty Chemicals, benzotriazole ultraviolet absorber,
(Note 9) “Adecanol UH438”: trade name, manufactured by Asahi Denka Co., Ltd., modified polyether urethane, viscosity modifier.

Production of aqueous paint composition for colored paint particles Production Example 6
The following components were sequentially blended in a container, and stirred and mixed so as to be uniform to obtain an aqueous coating composition (B-1) for colored coating particles.
Carbonyl group-containing emulsion (a1) 250 parts White pigment paste (b1) 154 parts 10% adipic acid dihydrazide aqueous solution 4 parts “TEXANOL” (Note 5) 20 parts “SN deformer 380” (Note 3) 2 parts “Adecanol UH-438 (Note 9) 2 parts 2% sodium alginate aqueous solution 280 parts.

Production Examples 7-8
In the above Production Example 6, water-based coating compositions (B-2) to (B-3) were produced in the same manner as in Production Example 6 except that the composition was changed to the composition shown in Table 2 below.

(Note 10) Red rust pigment paste (b2): The following components were charged into a 1 liter stainless steel container, and stirred with a disper for 30 minutes to obtain a red rust pigment paste (b2).
Water 520 parts Monoethylene glycol 40 parts “Slulloff 72N” (Note 1) 8 parts “DISPER BYK-190” (Note 2) 48 parts “SN Deformer 380” (Note 3) 16 parts Iron oxide 240 parts.

(Note 11) Black pigment paste (b3): The following components were charged in a stainless steel container of 1 liter and stirred with a disper for 30 minutes to obtain a black pigment paste (b3).
Water 520 parts Monoethylene glycol 40 parts “Slulloff 72N” (Note 1) 8 parts “DISPER BYK-190” (Note 2) 48 parts “SN Deformer 380” (Note 3) 16 parts Carbon black 200 parts.

Production of colored paint particles Production Example 9
A water-based coating composition obtained as described above was prepared by charging 1,300 parts of a 0.15% aqueous calcium hydroxide solution into a 4 liter stainless steel container and stirring at a rotational speed of 2500 rpm using a stirring blade having a diameter of 75 mm. (B-1) 650 parts were gradually dropped into the container to produce colored paint particles. Next, the liquid in the container was further stirred for 15 minutes at the same rotation speed, and then filtered using a 200-mesh wire mesh to obtain colored paint particles (C-1) having a solid content of 20%.

Production Examples 10-11
In Production Example 9, colored paint particles (C-2) to (C-2) to (C) are produced in the same manner as in Production Example 9 except that the aqueous paint composition shown in Table 3 below is used instead of the aqueous paint composition (B-1). C-3) was obtained.

Production of water-based clear paint for coating film forming component Production Example 12
The following components were charged in a 2 liter stainless steel container, and stirred and mixed with a stirrer for 30 minutes to obtain an aqueous clear coating material (c1) having a solid content of 50%.
Carbonyl group-containing emulsion (a1) 750 parts “TEXANOL” (Note 5) 50 parts Water 279 parts “Talc SS” (Note 12) 250 parts “SN Deformer 380” (Note 3) 10 parts “Adecanol UH-438” (Note) 9) 6 parts (Note 12) “Talc SS”: trade name, manufactured by Nippon Talc Co., Ltd.

Manufacture of water-based colorful pattern paint Production Examples 13-15
The components shown in the following Table 4 were charged into a 500 ml sterence vessel while sequentially stirring, and then stirred until uniform, thereby obtaining multicolored paints (D-1) to (D-3).

Preparation of test coated plates Examples 1-4 and comparative examples 1-2
On a slate plate (150 × 70 × 3 mm), “EP sealer transparent” (manufactured by Kansai Paint Co., Ltd., water-based acrylic emulsion sealer) was applied with a roller so that the coating amount was 100 g / m ² and dried. Each undercoat paint shown in Fig. 5 is roller-coated so that the coating amount is 100 g / m ² , dried for one day under conditions of an air temperature of 23 ° C and a relative humidity of 60%. Spray coating was performed at the coating amount shown in Table 5. Then, it dried for 7 days under the conditions of air temperature 23 degreeC and relative humidity 60%, each test coating board was obtained, and each test coating board was used for the following performance test. The results are also shown in Table 5. The concealment rate in the table is as follows. The concealment rate test paper described in Method B (Concealment rate test paper) of JIS K 5600 4-1 is fixed horizontally on a flat glass plate, and the various pattern paints on it. Is applied so as to have the coating amount shown in Table 5, the coated surface is leveled upward, and dried for 48 hours under conditions of an air temperature of 23 ° C. and a relative humidity of 60% to create a test piece for measuring the concealment rate, Randomly select four locations on the white and black ground of each test piece (coated coverage test paper), and set the tristimulus values for those locations to “CR-300” (trade name, manufactured by Minolta, color difference meter). ) was measured and calculated by calculating the average of the tristimulus values Y _W and Y _B.

(* 1) Appearance of coating film The coating film of each test coated plate was visually observed and evaluated according to the following criteria.
○: The brightness of the glitter pigment can be moderately recognized from the bottom of the multicolored paint film, and the design is excellent.
Δ: The brightness of the glitter pigment can be recognized from the bottom of the multicolored paint film, but it is insufficient.
X: The luster of the glitter pigment cannot be recognized from the bottom of the multicolored paint film, and the design is monotonous.

(* 2) Accelerated weather resistance According to JIS K 5600 7-7 (xenon lamp method), the test coated plate after 2000 hours was visually observed and evaluated according to the following criteria.
A: There is no luster and the glitter is good.
○: Slight luster is recognized, but there is a sense of brightness, practical level,
Δ: Glossiness and reduction in glitter are recognized,
X: A glittering feeling is not recognized.

Claims (8)

On the glitter coating film formed by applying the paint (I) containing the glitter pigment, the pigment composition comprises the colored paint particles (A) and the coating film forming component (B), and the colored paint particles (A) A multi- pattern paint (II), which is formed by encapsulating a water-based resin composition (a1) and a colorant (a2) in a polysaccharide metal salt gel, is provided with a multi-pattern paint film. A method for forming a designable coating film, comprising: coating the multicolored paint (II) so that a concealing rate of the formed coating film is within a range of 10 to 70%. Method. The design coating film according to claim 1, wherein the paint (I) containing the glitter pigment contains the glitter pigment within a range of 0.01 to 100% by mass with respect to a resin solid content contained in the paint (I). Forming method. The design coating film forming method according to claim 1 or 2, wherein the paint (I) containing the glitter pigment further contains a color pigment. The design coating film forming method according to any one of claims 1 to 3, wherein the paint (I) containing the glitter pigment further contains an ultraviolet absorber and / or a light stabilizer. Monovalent in which the colored coating particles (A) can form an aqueous coating composition containing the aqueous resin (a1), the colorant (a2) and the water-soluble polysaccharide, with the water-soluble polysaccharide and a water-insoluble or hardly soluble salt. The method for forming a designable coating film according to any one of claims 1 to 4, which is obtained by contacting with an aqueous medium containing a polyvalent metal ion. The colored coating particle (A) contains a reactive functional group (x), and the coating film forming component (B) contains a reactive functional group (y) that can react with the reactive functional group (x). The method for forming a designable coating film according to any one of claims 1 to 5 . Both the colored paint particles (A) and the coating film forming component (B) contain a carbonyl group-containing aqueous resin, and the colored paint particles (A) and / or the coating film forming component (B) contain a hydrazine derivative. The method for forming a designable coating film according to any one of claims 1 to 6 . The coating-film structure excellent in the designability obtained by the designable coating-film formation method of any one of Claim 1 thru | or 7.